Triphenylmethane polymeric colorant having sterically hindered amine counter ions

ABSTRACT

Triphenylmethane dyes or colorants with sterically hindered fugitive amine counter ions are provided as durable, storage-stable, and excellent coloring and shading printing inks. Ink compositions are disclosed which provide improvements in long-term storage capabilities, particularly within alkaline environments, extremely effective colorations of cellulose-based substrates, and lower cost over those of the prior art. The preferred dyes or colorants are triphenylmethane polymeric colorants which are capped with cyclic anhydride and the preferred sterically hindered amine counter ions are those based on low molecular weight fugitive tertiary amines, such as N,N-dimethylethanolamine. Compositions comprising water soluble or emulsion resins as diluents for lowered viscosity and lower overall cost are also contemplated. Furthermore, compositions comprising the inventive colorant and other pigments, dyes, surfactants, preservatives, and other colorants are contemplated. A method of making such an inventive ink composition and a cellulose-based substrate contacted with such an inventive ink composition are also disclosed.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of application Ser. No. 09/484,921,filed on Jan. 18, 2000 allowed, which is a continuation of applicationSer. No. 09/024,208, filed on Feb. 17, 1998, now U.S. Pat. No.6,063,175.

FIELD OF THE INVENTION

This invention relates to triphenylmethane compounds for aqueous inkformulations which are storage stable for prolonged periods of timeunder alkaline conditions. Preferably, these compounds are eitherdyestuffs or polymeric colorants. Methods of making and using suchaqueous inks are also contemplated within this invention.

DISCUSSION OF THE PRIOR ART

Triphenylmethane chromophore-based inks, particularly those dyes orcolorants capped with cyclic anhydride, are well known for theirexcellent ability for coloring and shading within the printing industry.Problems exist, however, during the storage of such triphenylmethanes.Upon contact with an alkaline storage environments, chemicalrearrangement may occur rendering undesirable shades. For instance, withtriphenylmethane colorants, this degradation of color apparently occursdue to the presence of terminal carboxylic anions of a polymericchromophore neutralized with hydroxide, ammonia, ethanolamine,diethanolamine, or other unhindered amines. This degradation of colorresults in very short storage time or requires refrigerated storage, allof which increases the costs associated with colorant storage. Animproved cost-effective method of storing such colorants withsubstantially no shade degradation is thus necessary within the printingindustry.

Triphenylmethane dyes and colorants, and, again, particularly thosewhich are capped with cyclic anhydride, are well known within theprinting industry and have been taught within U.S. Pat. No. 4,871,371,to Harris, and U.S. Pat. No. 5,310,887, to Moore et al., the disclosuresof which are herein entirely incorporated by reference. Such compounds,as noted above, must undergo neutralization of their terminal carboxylicacids with a counter ion in order to provide solubility within anaqueous medium. Again, the problem with such a step is the degradationof suitable printing shades after reaction with common alkaline counterions. It is believed that this undesired reaction is the result ofinterference from the primary or secondary amine moieties of the counterion (neutralizing compound), such as diethanolamine, monoethanolamine,and the like, for example, or the strong nucleophilicity of alkali metalhydroxide ions, alkaline earth metal hydroxide ions, ammonium ions, andzinc ammonium complexes, or the resultant carboxylates of these ions andcomplexes, all being present in stoichiometric proportions, when used assuch a counter ion. Thus, again, there is a need to provide a relativelyinexpensive storage stable aqueous ink composition comprisingtriphenylmethane polymeric colorants, including cyclic anhydride cappedcolorants. The prior art has not accorded such an improvement to theprinting industry.

DESCIPTION OF THE INVENTION

It is thus an object of the invention to provide an improved aqueous inkcomposition comprising triphenylmethane dyes or colorants. A furtherobject of the invention is to provide a relatively inexpensive,improved, storage-stable (particularly under alkaline conditions)triphenylmethane-based polymeric colorant for the printing industry.Another object of the invention is to provide a printing ink havingpleasing coloring and shading characteristics and having substantiallyno color degradation after a prolonged storage period, particularlyunder standard alkaline conditions. Yet another object of this inventionis to provide a process for making such an improved coloringcomposition, as well as a method of using such a triphenylmethanepolymeric colorant for printing cellulose-based writing surfaces,particularly newspapers, commercial inserts, folding cartons, householdpaper products, multiwall paper bags, and corrugated containers, merelyas examples. One further object is to provide an improved long-lastingstorage-stable aqueous printing ink composition comprising cyclicanhydride-capped triphenylmethane polymeric colorants and methods ofmaking and using such a composition.

Accordingly, this invention concerns an aqueous ink compositioncomprising a triphenylmethane dye or colorant neutralized with asterically hindered amine counter ion. Preferably, the triphenylmethanecompound is a polymeric colorant containing carboxylic acid groupsneutralized with a sterically hindered amine counter ion. The termpolymeric is meant to include those colorants which have alkylene oxidechains reacted with cyclic anhydrides and attached to nucleophilicgroups bonded to the triphenylmethane backbone. The preferred alkyleneoxides are ethylene oxide, propylene oxide, and butylene oxide, and anymixtures thereof. Ethylene oxide provides greater degrees watersolubility for the colorant. Lower levels of such solubility arepossible with greater numbers of longer chain alkylene oxide moieties.Preferred nucleophilic bridging groups include amino, hydroxyl, thio, orany other well known bridging group for alkylene oxides to achromophore, such as those listed within U.S. Pat. No. 5,310,887.Preferred cyclic anhydrides are those ranging in chain length from aboutC₂ to about C₃₀.

The sterically hindered amine is one of a low molecular weight fugitivetertiary amine. The tertiary structure of the amine counter iondecreases its ability to act as a strong nucleophilic agent attackingany reactive centers of the chromophore. This fugitive tertiary amine isgenerally selected from the group consisting of one or more ofdi(C₁-C₁₀-alkyl)ethanolamine. Examples of such amines include and arepreferably N,N-dimethylethanolamine, N,N-diethylethanolamine,N,N-dipropylethanolamine, N-methyl-N-ethylethanolamine,N-methyl-N-propylethanolamine, and the like. This list is not meant tolimit the invention in any way as any number of other low molecularweight fugitive sterically hindered amines may be suitable as counterions. The low molecular weight and fugitivity requirement for such atertiary amine counter ion facilitates its evaporation upon utilizationin a standard printing method. In order to produce water fast colors ona cellulose-based substrate (i.e., paper), the triphenylmethanepolymeric colorants must be effectively free of their counter ions. Theterm fugitivity means the removal of amine counter ion which isaccomplished through evaporation upon long-term presence within a dryenvironment, through neutralization of the amine on the cellulose-basedsubstrate itself (i.e., paper surfaces are generally acidic due to thepresence of alum), or through the migration of the counter ion withinthe paper substrate. The removal of counter ion is accomplished throughany of these three processes. Nowhere within the prior art is such asterically hindered amine counter ion either taught or fairly suggestedas a manner to reduce the effect of alkaline degradation upon thecoloring and shading ability of a triphenylmethane polymeric colorant.

Any triphenylmethane dye or colorant is contemplated within thisinvention; however, the preferred types are those which are polymericcolorants and capped with cyclic anhydride. Particularly preferredcyclic anhydride capped triphenylmethane polymeric colorants are taughtwithin U.S. Pat. No. 5,310,887, to Moore et al., mentioned above, andare represented by the formula:

A—{Y—X—C(O)—R—C(O)O⁻}_(p)

wherein A is a triphenylmethane organic chromophore; Y is apolyoxyalkylene substituent; X is a radical of a reactive hydroxyl,amino, or thio group; R is C₂₋₃₀, substituted or unsubstituted alkylene,alkyenylene, or phenylenealkylene; and p is from 1 to 4, and preferably4. In general, when in aqueous composition, the sterically hinderedfugitive amine counter ion is present in an amount of from about 0.01 toabout 15% by parts of the entire amount of the triphenylmethane dye orcolorant within the composition; preferably this amount is from about 1to about 12%; more preferably from about 4 to about 8%; and mostpreferably from about 5 to about 7%.

Any other standard ink composition additives, such as resins,preservatives, other colorants, dyes, pigments, surfactants, andantistatic compounds may also be incorporated within the inventivecomposition or utilized within the inventive method. In fact, it ispreferred that the inventive ink compositions include at least oneadditive selected from the group consisting essentially of a pigment, asurfactant, a preservative, an antistatic compound, another dye, andanother colorant (that is, other than the inventive triphenylmethane dyeor colorant), and any mixtures thereof. The inventive dye or colorantmay provide a supplement to other pigments, dyes, and colorants, inorder to produce excellent reproductions of photographs, pictures, andthe like, on paper substrates. The optional pigments, other dyes, andother colorants may be of any suitable class, including anionic dyes,reactive dyes, and the like, and compounds comprising at least one ofthe following substituent groups: azo, including polyazo,diphenylmethane, triarylmethane, xanthene, methine, includingpolymethine, acridine, quinoline, thiazole, indamine, indophenol, azine,oxazine, thiazine, anthraquinone, indigoid and phthalocyanine, furtherincluding poly(oxyalkylene) derivatives of the above-listed compounds.The optional surfactants may be those well known in the art as anionic,cationic, amphoteric, and zwitterionic in nature. Optional preservativesinclude any well known examples of such compounds within inkcompositions, such as Nuosept® 95, manufactured by Huls America, andKathon® GC/ICP, manufactured by Rohm and Haas.

Particularly desired as optional additives are water solution oremulsion resins which are present to adjust the viscosity of and toincrease the film strength of the ultimate ink formulations. Such resinsinclude acrylics, acrylic latexes, proteins, and urethanes. Of limiteduse due to their low degree of water solubility, but feasible as resinsfor this composition, are carboxylated acrylics, polyvinyl alcohol,hydroxyethyl cellulose, and polyvinyl pyrrolidone. These resins arepreferably acrylic in nature and comprise from 0 to about 40% of theentire ink composition. Particularly preferred acrylic resins areacrylic solution resins, such as Joncryl® 60, manufactured by S.C.Johnson & Son, Inc., Morcryl® 132 and 150, manufactured by MortonInternational, Inc.; acrylic emulsion resins, such as Joncryl® 537, 540,1954, SCX-2153, and SCX-2155, manufactured by S.C. Johnson & Son, Inc.;styrenated acrylic emulsion resins, such as Joncryl® 89 and 130,manufactured by S.C. Johnson & Son, Inc., Lucidene® 602, manufactured byMorton International, Inc., and Zinpol® 460, manufactured by B.F.Goodrich; acrylic colloid emulsion resins, such as Joncryl® 142 andSCX-646, manufactured by S.C. Johnson & Son, Inc.,; acrylic copolymeremulsion resins, such as NeoCryl® XA-590 and B-817, manufactured by ICIResins; and polyester-styrene acrylic resins, such as Lucidene® 1500,manufactured by Morton International, Inc.. The most preferred acrylicresin is Joncryl® 130, a styrenated acrylic emulsion manufactured byS.C. Johnson & Son, Inc., which increases water fastness. These resinsare generally neutralized with ammonia to increase their aqueoussolubility. Interestingly, this ammonia neutralization does not affectthe stability and colorability of the inventive triphenylmethaneproduct, and, in particular, does not affect the preferred polymericcolorant, upon association with the sterically hindered amine counterion. Even after a long storage period (13 months) at elevatedtemperatures of about 100° F. and at pH levels of between 7.5 and 8.5,such resin-diluted water soluble ink compositions showed no loss ofcolor or shade change. At a lower pH level (below 7.0), the colorantshowed a neutralization of carboxylic acids, resulting in a loss ofwater solubility. At pH levels above 8.5, the esters formed by reactionof the alkylene oxide moieties and the cyclic anhydrides undergohydrolysis, resulting in loss of waterfastness. Also with regard to thepotential resin constituents of the inventive compositions are thosewhich have a low viscosity to provide the most effective depth of coloron the printing substrate. Preferably, the resin is present in an amountsufficient to provide an ink composition having a viscosity, as testedusing a #2 Shell Cup, ranging from about 16 to about 26 seconds, andmost preferably from about 22 seconds. This amount generally comprisesfrom about 5 to about 40 wt % of the total ink composition. Also ofgreat importance to this inventive composition is the utilization ofsoftened or deionized water to dilute the thick liquid colorant beforeformulating an ink composition. Hard or tap water may contain calcium orother metal ions which may complex with the aforementioned resins,effectively increasing the overall viscosity of the composition.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The preferred method of making the preferred inventive colorant is asfollows:

Aniline was reacted with 2 moles of ethylene oxide followed by 13 molesof propylene oxide. The polyoxyalkylenated aniline derivative wascondensed with o-formyl benzenesulfonic acid, oxidized, and washed togive a dark blue colorant, as is well known in the art. Water was thenremoved from the polymeric colorant by heating under vacuum to give 504parts of dry material. To the dry blue colorant was added 276 parts ofdodecenyl succinic anhydride and 4 parts of 1-methylimidazole (acatalyst). The mixture was heated to 190° F. with stirring and held atthat temperature for three (3) hours. The heating was continued untilthe measured anhydride peak at 1880^(−cm) within the infrared spectrumhad disappeared. The resultant composition was a thick blue liquid. Tothis viscous liquid was added 670 parts of demineralized water whilestirring, followed by 72.5 parts of N,N-dimethylethanolamine. Thisresultant composition was equal to 1480 parts of a soluble dark bluepolymeric triphenylmethane colorant. The colorant had a viscosity at 25°C. of 1540 cps (measured by a Brookfield DV-II viscometer at an RVspindle rate of 60 rpm) had a pH of 7.0, and had a color value of 16.53(measured with a Beckmann DU7 UV visible spectrophotometer; abs/g/L inmethanol) with λ_(max) at 628 nm.

Samples of this colorant were then incorporated into a variety ofdifferent ink compositions for comparison tests, as described in greaterdetail below. Samples of each ink composition were stored in sealedglass vials in an oven at 122° F. Periodically, the ink samples wereremoved from the oven, allowed to cool to room temperature, and appliedto a substrate. Specifically, each ink composition sample was drawn downwith a Pamarco 360 cell count hand proofer, tool reference 155, on whiteprinting grade newsprint purchased from Dillard paper, #VB595. Printdensities for all of the samples were 1.0 on the density T scale. Printsamples were analyzed with an Xrite® Model 938 Spectrodensitometer usingCIELAB coordinates. The spectrodensitometer was adjusted to thefollowing settings: 10 degree viewer, D65 illuminant, and 4 mm measuringdiameter. The instrument was calibrated with a standard white tile.

The following examples are thus indicative of the preferred embodiments,both the compositions and methods, of this invention:

EXAMPLE 1

An ink composition was then produced by diluting the liquid colorantwith an equal number of parts of deionized water and adjusting the pHwith dimethylethanolamine (DMEA) to about 8.0. Subsequently added wasabout 148 parts of a styrenated acrylic emulsion resin, Joncryl® 130,and small amounts (about 10 parts each) of biocide preservatives,Nuosept® 95, manufactured by Huls America, and Kathon® GC/ICP,manufactured by Rohm and Haas, as well as further amounts of deionizedwater and DMEA to obtain the correct 8.0 pH level. The overall viscosityof the ink composition, using a #2 Shell Cup, was about 22 seconds. (Theuse of deionized water is necessary to avoid an increase in viscositydue to complexing with calcium or other ions within hard, tap water.Also, any well known preservative is contemplated as an additive withinthe inventive composition.)

This ink composition was stored in a standard alkaline storagecomposition within a standard storage ink container for 13 months at atemperature of 122° F. Periodically, as well as after this prolongedperiod of time, the ink composition was tested utilizing the same basicpaper marking test and showed no change in shade or loss of color fromthe initial test, the results of which are tabulated below.

EXAMPLE 2

An ink composition was produced by diluting the liquid colorant withoutthe subsequent addition of a resin composition, in contrast toEXAMPLE 1. This composition also had a viscosity of about 22 secondsutilized a #2 Shell Cup test. The non-resin containing sample showedexcellent coloring and shading in the paper draw down test. Upon 13months of storage at a pH level of about 8.0 and at a temperature ofabout 122° F., the ink composition showed no loss in color ordegradation of shade, again, through the same draw down test, theresults of which are indicated below.

EXAMPLES 3-5 Comparative

Ink compositions were also produced by diluting the liquid colorant withan equal number of parts of deionized water and adjusting the pH with avariety of bases (counter ions), including aqueous ammonia (EXAMPLE 3),ethanolamine (EXAMPLE 4), and diethanolamine (EXAMPLE 5), to 8.0. Theviscosity of each ink composition equaled about 22 seconds, measuredwith a #2 Shell Cup. Ink samples were drawn down using the sameprocedure and substrate as with EXAMPLES 1 and 2, above.

All of the ink samples, including those produced in EXAMPLES 1 and 2,were tested for their color stability after long storage periods in anoven. The color difference between the initial print and print from inkthat was oven aged was calculated for each sample using the followingequation:

ΔE*=((L* _(initial) −L* _(aged))²+(a* _(initia) l+a* _(aged))²+(b*_(initial) −b* _(aged))²)½

wherein ΔE* represents the difference in color between the initialprinted sample and the sample printed with oven aged ink. L*, a*, and b*are the color coordinates; wherein L* is a measure of the lightness anddarkness of the print sample; a* is a measure of the redness orgreenness of the print sample; and b* is a measure of the yellowness orblueness of the print sample. For a further discussion and explanationof this testing procedure, see Billmeyer, F. W., et al., Principles ofColor Technology, 2nd Edition, pp. 62-64 and 101-04. The results forEXAMPLES 1-5 are presented in tabulated form below:

TABLE ΔE* Calculations for EXAMPLES 1-5 EXAMPLE # ΔE* for 3 Weeks ΔE*for 56 Weeks Correlative To Neutralizing Base Storage at 122° F. Storageat 122° F. 1-Dimethylethanolamine in 0.91 1.61 10% acrylic resin2-Dimethylethanolamine 0.47 1.77 3-Aqueous Ammonia 20.64 *4-Ethanolamine 5.67 * 5-Diethanolamine 6.27 * *No ΔE* could accuratelybe measured for these samples since the change in color through visualobservation alone indicated a drastic alteration of color.

Clearly, the sterically hindered tertiary amine counter ions(neutralizing bases) provide the best stability for the triphenylmethanepolymeric colorant, particularly over long-term, high temperaturestorage.

There are, of course, many alternative embodiments and modifications ofthe present invention which are intended to be included within thespirit and scope of the following claims.

What I claim is:
 1. A cellulose-based substrate, at least a portion ofwhich is contacted with a triphenylmethane polymeric colorant whereinsaid colorant has a sterically hindered fugitive amine counter ionselected from di(C₁-C₁₀)alkyl)ethanolamin.
 2. The cellulose-basedsubstrate of claim 1 wherein said fugitive amine counter ion isdimethylethanolamine.